Vat dyestuffs



Patented Oct. 6 1931 1 UNITED PATENT OFFICE MAXALBERT KUNZ, or MANN-1mm, AND KAR xoEBERLE, D FLUGWIGS HAFEN-ION- THE-RHINE, GERMANY, ASSIGNORS GENERAL ANILINE WoRKs, INC .015 NEW a No vlfn'awing.

i YORK, fNi' Y .A CORPORATIONOFTDELAWARE VAT :DYESTUFFS The present invention relates to new Wat dyestuffs.

We have found that valuabledyestufisdyeing the vegetable fibre from the vat grey shades of excellent fastness and great strength are obtained by condensing 1 molecular proportion of a 3.l.8.9dibenzopyrene- 5.10-quinone containing from 1 to it-halogen atoms With from 1 to 4'molecular proportions of l-amino-t-benzoylamino anthraquinone. Since in the said condensation halogen hydride is split off, the resultingproducts correspond to the general formula wherein n is 1, 2, '3 01-4. Thesame products can also be obtainedby employing 1.4-diamino anthraquinone in such proportions as to combine only one-amino group thereof with the dibenzopyrenequinone molecule an'dthen benzoylating the remaining amino group of the diamino anthraquinone radical. The

v dyestuffs obtained according tdth'e present invention are greyto-black powders dissolving' in concentrated sulphuric aci'd 'with red'to blue red color and dyeing cotton from a brown red vat grey shades of excellent fast-' ness. Particularly valuable are'those products which are obtained from the 'dih-alogen- Application fildMarCh 15, 1929'. ,Seria1N'o.347;445.

dibenzopyrene quinones because these part cularly, fast and have a particularly great tinctorial strength, and thosejp'r oducts which are derived from the dibromo-3A.8.9

diben'z'opyrene 5.10-qui'none obtainable b dissolving 33 parts of pure 3.4i8;9-dibenzo' pyr'ene-'5.10,-quinone in 300parts of "chl'oro' sulph'on'ic acidyadding-from 1.65 to 2.3 parts of iodine and then at room temperature 20 parts'of bromine; and heating to'from '7 0 to 80 untilthe bulk of the brmnine has been takenup {the constitutionof this produc'tis' probably as follows), V .y

are the :most valuable dyestufl's.

When :the new products are-treated with acid condensing 1 agents, such as aluminium chloride or;a imixture: of -aluminium chloride andsodium chloride formationv of. a carbazol nucleus talges place and :new dyestuffs are obtained which are only diflicultly soluble in concentrated sulphuric acid giving green blue solutions and which dye the fibre eryrast bmwn shades.

The following examples will further ill'us t'rate'howbur present "invention maybe car-j I'ied-out in practice; "but-the invention 'is not limited to these examples; The parts are by Weight. 1

Ewawzple J. i

98 parts of the-dibrom'o-34.8.9-dibenzopyrene-i5;10-quinone vspecifically referred to abovecare boiledin 1200 partsof naphthalene with l0Q';-parts of calcined sodium carbonate, 10 parts of copper oxide and 141 parts oil amino-4-benzoylaminoanthraquinone5 while et le,

stirring, until the reaction product is practically free from bromine. The product may be worked up by diluting the mixture, after cooling it to about 130 to 140 C., with 1500 parts of monochlorobenzene, filtering by suction and treating the residue with steam in order to remove the last traces of solvent, or by distilling off the solvent, if desired with the aid of a vacuum or of steam or both. The resulting dyestuil which is obtained with a good yield and in a state of high purity, is a bluish grey powder dissol *ing to a bluish red solution in concentrated sulphuric acid and dyeing cotton from a brown red vat strong bluish grey shades of excellent fastness and in particular absolute i astness to boiling with soap or soda solution, to chlorine and to bucking.

Instead of the aforesaid dibromo-dibenzopyrenequinone, an equivalent amount of the corresponding diehloroor diiodo-derivative may be used. The naphthalene can be replaced by other solvents or suspension media, for example by nitrobenzene, but the reaction may also be carried out in the absence of such agents. Instead of sodium carbonate, other salts of the alkali metals or alkaline earth metals or the oxides of the last group of metals may be used as agents binding acids, and the copper oxide may be replaced by metallic copper or by other copper compounds.

Emample 2 ll parts of monobromo-det.8.9-dibenzopyrene-alU-quinone (obtainable, for example, by oroniinating 2i.at.6.ti-dibenzopyrenepdd quinone 111 chlorosulphonic acid with the aid ut iodine as a catalyst) are boiled in ace parts or nitrouenzene with 50 parts 01 sodium ace- Late, -l parts or copper carbonate and 50 parts or i-annno-a-benzoylannno antnraquinone, while stirring, until the reaction product is practically tree trom bromine. The product is worked up as described in Example l. The resulting dyestuli is a black powder dissolving to a red solution in concentrated sulphuric acid and dyes cotton from a brown red vat grey shades of excellent tastness. Instead of the aforesaid inonobromo-dibenzopyrenequinone, an equivalent amount of other inonohalogen 3.l.8.9 dibenzopyrene- 5.10-quinones may be used, and the process may be carried out in naphthalene instead of in nitrobenzene, or also in the absence of solvents or suspension media.

Example 3 49 parts of the dibro1no-3. l.8.9-dibenzopyrene-5.10-quinone used according to Example 1 are boiled in 500 parts of naphthalene, while stirring, with 50 parts of 1.4-

diamino-anthraquinone, 50 parts of calcined sodium carbonate and 5 parts of copper carbonate, until the reaction product is practically free from bromine. The product may be worked up as described in Example 1 and then benzoylated by one of the usual methods. Or the reaction mixture is allowed to cool to about 100 C. whereupon 10 parts of collidine and 25 parts of benzoyl chloride are added and the mixture is heated to from 180 to 200 C. until a sample gives a dyeing on cotton, which is completely fast to chlorine. The product is identical with that described in Example 1.

The product described in Example 2 can be prepared in an analogous manner.

\Vhat we claim is:

1. As new articles of manufacture, the vat dyestuffs corresponding to the general formula museum;

which dyestulis are bluish grey to bluish black powders dissolving to blue red solutions in concentrated sulphuric acid and dye cotton from brown red vats strong bluish grey shades of excellent fastness.

3. As a new article of manufacture, the Vat dyestulf corresponding to the formula no l A O (H) which dyestufl is a bluish grey powder dissolving to a blue red solution in concentrated sulphuric acid, dyes cotton from a brown red vat strong bluish grey shades of excellent fastness, and which is obtainable by condensing two molecular proportions of 1- amino4-benzoylamino-anthraquinone with one molecular proportion of the dibromo- 3.4.8.9-dibenzopyrene-5.10-quinone obtainable by dissolving 33 parts of pure 3.4.8.9- dibenzopyrene-5.10-quinone in 300 parts of chlorosulphonic acid, adding from 1.65 to 2.3 parts of iodine and then at room temperature 20 parts of bromine, and heating to from to C. until the bulk of the bromine has been taken up.

4. The process of producing new Vat dyestuffs which comprises condensing one molecular proportion of a 3.4.8.9-dibenzopyrene- 5.10-quin0ne containing from 1 to 4; halogen atoms with as many molecular proportions of 1.4-diamino anthraquinone, as halogen atoms are present in the dibenzopyrenequinone molecule, and benzoylating the resulting product.

5. The process of producing new vat dyestuffs which comprises condensing one molecular proportion of dihalogen-3A.8.9-dibenzopyrene-5.10-quinone with 2 molecular proportions of 1.4-diaminoanthraquinone, and benzoylating the resulting product.

In testimony whereof we have hereunto set our hands.

MAX ALBERT KUNZ. KARL KOEBERLE. 

